Lesson

14
Vapour Absorption
Refrigeration Systems
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The objectives of this lesson are to:
1. Introduce vapour absorption refrigeration systems (Section 14.1)
2. Explain the basic principle of a vapour absorption refrigeration system
(Section 14.2)
3. Compare vapour compression refrigeration systems with continuous vapour
absorption refrigeration systems (Section 14.2)
4. Obtain expression for maximum COP of ideal absorption refrigeration system
(Section 14.3)
5. Discuss properties of ideal and real refrigerant-absorbent mixtures (Section
14.4)
6. Describe a single stage vapour absorption refrigeration system with solution
heat exchanger (Section 14.5)
7. Discuss the desirable properties of refrigerant-absorbent pairs for vapour
absorption refrigeration systems and list the commonly used working fluids
(Section 14.6)

At the end of the lecture, the student should be able to:

1. List salient features of vapour absorption refrigeration systems and compare

them with vapour compression refrigeration systems
2. Explain the basic principle of absorption refrigeration systems and describe
intermittent and continuous vapour absorption refrigeration systems
3. Find the maximum possible COP of vapour absorption refrigeration systems
4. Explain the differences between ideal and real mixtures using pressure-
composition and enthalpy-composition diagrams
5. Draw the schematic of a complete, single stage vapour absorption refrigeration
system and explain the function of solution heat exchanger
6. List the desirable properties of working fluids for absorption refrigeration
systems and list some commonly used fluid pairs

14.1. Introduction
Vapour Absorption Refrigeration Systems (VARS) belong to the class of
vapour cycles similar to vapour compression refrigeration systems. However, unlike
vapour compression refrigeration systems, the required input to absorption systems is
in the form of heat. Hence these systems are also called as heat operated or thermal
energy driven systems. Since conventional absorption systems use liquids for
absorption of refrigerant, these are also sometimes called as wet absorption systems.
Similar to vapour compression refrigeration systems, vapour absorption refrigeration
systems have also been commercialized and are widely used in various refrigeration
and air conditioning applications. Since these systems run on low-grade thermal
energy, they are preferred when low-grade energy such as waste heat or solar energy
is available. Since conventional absorption systems use natural refrigerants such as
water or ammonia they are environment friendly.

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 In this lesson, the basic working principle of absorption systems, the maximum
COP of ideal absorption refrigeration systems, basics of properties of mixtures and
simple absorption refrigeration systems will be discussed.

14.2. Basic principle

When a solute such as lithium bromide salt is dissolved in a solvent such as
water, the boiling point of the solvent (water) is elevated. On the other hand, if the
temperature of the solution (solvent + solute) is held constant, then the effect of
dissolving the solute is to reduce the vapour pressure of the solvent below that of the
saturation pressure of pure solvent at that temperature. If the solute itself has some
vapour pressure (i.e., volatile solute) then the total pressure exerted over the solution
is the sum total of the partial pressures of solute and solvent. If the solute is non-
volatile (e.g. lithium bromide salt) or if the boiling point difference between the
solution and solvent is large (≥ 300oC), then the total pressure exerted over the
solution will be almost equal to the vapour pressure of the solvent only. In the
simplest absorption refrigeration system, refrigeration is obtained by connecting two
vessels, with one vessel containing pure solvent and the other containing a solution.
Since the pressure is almost equal in both the vessels at equilibrium, the temperature
of the solution will be higher than that of the pure solvent. This means that if the
solution is at ambient temperature, then the pure solvent will be at a temperature
lower than the ambient. Hence refrigeration effect is produced at the vessel containing
pure solvent due to this temperature difference. The solvent evaporates due to heat
transfer from the surroundings, flows to the vessel containing solution and is absorbed
by the solution. This process is continued as long as the composition and temperature
of the solution are maintained and liquid solvent is available in the container.

For example, Fig.14.1 shows an arrangement, which consists of two vessels A

and B connected to each other through a connecting pipe and a valve. Vessel A is
filled with pure water, while vessel B is filled with a solution containing on mass
basis 50 percent of water and 50 percent lithium bromide (LiBr salt). Initially the
valve connecting these two vessels is closed, and both vessels are at thermal
equilibrium with the surroundings, which is at 30oC. At 30oC, the saturation pressure
of water is 4.24 kPa, and the equilibrium vapour pressure of water-lithium bromide
solution (50 : 50 by mass) at 30oC is 1.22 kPa.

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a) Initial condition
U

Valve closed

4.24 kPa 1.22 kPa

Water at 30oC 50% LiBr soln. at 30oC

A
Water vapour
o
30 C

30oC
b) Refrigeration Valve open

1.22 kPa 1.22 kPa

Water at 10oC 50% LiBr soln. at 30oC

Qe A B Qc
Water vapour

c) Regeneration

Valve open

4.24 kPa 4.24 kPa

Water at 30oC Weak LiBr soln. at Tg

Qc Qg
o
30 C

Tg > To > Te

Fig.14.1: Basic principle of vapour absorption systems

Thus at initial equilibrium condition, the pressure in vessel A is 4.24 kPa,
while it is 1.22 kPa in vessel B. Now the valve between vessels A and B is opened.
Initially due to pressure difference water vapour will flow from vessel A to vessel B,
and this vapour will be absorbed by the solution in vessel B. Since absorption in this
case is exothermic, heat will be released in vessel B. Now suppose by some means the
concentration and temperature of vessel B are maintained constant at 50 % and 30oC,
respectively. Then at equilibrium, the pressure in the entire system (vessels A and B)
will be 1.22 kPa (equilibrium pressure of 50 % LiBr solution at 30oC). The

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temperature of water in vessel A will be the saturation temperature corresponding to
1.22 kPa, which is equal to about 10oC, as shown in the figure. Since the water
temperature in A is lower than the surroundings, a refrigeration effect (Qe) can
produced by transferring heat from the surroundings to water at 10oC. Due to this heat
transfer, water vaporizes in A, flows to B and is absorbed by the solution in B. The
exothermic heat of absorption (Qa) is rejected to the surroundings.

Now for the above process to continue, there should always be pure water in
vessel A, and vessel B must be maintained always at 50 percent concentration and
30oC. This is not possible in a closed system such as the one shown in Fig.14.1. In a
closed system with finite sized reservoirs, gradually the amount of water in A
decreases and the solution in B becomes diluted with water. As a result, the system
pressure and temperature of water in A increase with time. Hence the refrigeration
effect at A reduces gradually due to the reduced temperature difference between the
surroundings and water. Thus refrigeration produced by systems using only two
vessels is intermittent in nature. In these systems, after a period, the refrigeration
process has to be stopped and both the vessels A and B have to be brought back to
their original condition. This requires removal of water absorbed in B and adding it
back to vessel A in liquid form, i.e., a process of regeneration as shown in Fig.14.1(c).

Assume that before regeneration is carried out, the valve between A and B is
closed and both A and B are brought in thermal equilibrium with the surroundings
(30oC), then during the regeneration process, heat at high temperature Tg is supplied
to the dilute LiBr solution in B, as a result water vapour is generated in B. The vapour
generated in B is condensed into pure water in A by rejecting heat of condensation to
the surroundings. This process has to be continued till all the water absorbed during
the refrigeration process (14.1(b)) is transferred back to A. Then to bring the system
back to its original condition, the valve has to be closed and solution in vessel B has
to be cooled to 30oC. If we assume a steady-flow process of regeneration and neglect
temperature difference for heat transfer, then the temperature of water in A will be
30oC and pressure inside the system will be 4.24 kPa. Then the temperature in vessel
B, Tg depends on the concentration of solution in B. The amount of heat transferred
during refrigeration and regeneration depends on the properties of solution and the
operating conditions. It can be seen that the output from this system is the
refrigeration obtained Qe and the input is heat supplied to vessel B during vapour
regeneration process, Qg.

The system described may be called as an Intermittent Absorption

Refrigeration System. The solvent is the refrigerant and the solute is called as
absorbent. These simple systems can be used to provide refrigeration using renewable
energy such as solar energy in remote and rural areas. As already explained, these
systems provided refrigeration intermittently, if solar energy is used for regenerating
the refrigerant, then regeneration process can be carried out during the day and
refrigeration can be produced during the night.

Though the intermittent absorption refrigeration systems discussed above are

simple in design and inexpensive, they are not useful in applications that require
continuous refrigeration. Continuous refrigeration can be obtained by having a
modified system with two pairs of vessels A and B and additional expansion valves
and a solution pump.

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 Qg at Tg
Qc at To Qc at To
Condenser Wc Condenser Generator
Pc
Pc Wp

Exp.device Exp.device Pe Pump Exp.device

Pe
Evaporator Evaporator Absorber

Qe at Te
Mechanical Thermal Qa at To
compression compression

a) VCRS b) VARS

Figs.14.2: a) Vapour compression refrigeration system (VCRS)

b) Vapour Absorption Refrigeration System (VARS)

Figure 14.2(a) and (b) show a continuous output vapour compression

refrigeration system and a continuous output vapour absorption refrigeration system.
As shown in the figure in a continuous absorption system, low temperature and low
pressure refrigerant with low quality enters the evaporator and vaporizes by producing
useful refrigeration Qe. From the evaporator, the low temperature, low pressure
refrigerant vapour enters the absorber where it comes in contact with a solution that is
weak in refrigerant. The weak solution absorbs the refrigerant and becomes strong in
refrigerant. The heat of absorption is rejected to the external heat sink at To. The
solution that is now rich in refrigerant is pumped to high pressure using a solution
pump and fed to the generator. In the generator heat at high temperature Tg is
supplied, as a result refrigerant vapour is generated at high pressure. This high
pressure vapour is then condensed in the condenser by rejecting heat of condensation
to the external heat sink at To. The condensed refrigerant liquid is then throttled in the
expansion device and is then fed to the evaporator to complete the refrigerant cycle.
On the solution side, the hot, high-pressure solution that is weak in refrigerant is
throttled to the absorber pressure in the solution expansion valve and fed to the
absorber where it comes in contact with the refrigerant vapour from evaporator. Thus
continuous refrigeration is produced at evaporator, while heat at high temperature is
continuously supplied to the generator. Heat rejection to the external heat sink takes
place at absorber and condenser. A small amount of mechanical energy is required to
run the solution pump. If we neglect pressure drops, then the absorption system
operates between the condenser and evaporator pressures. Pressure in absorber is
same as the pressure in evaporator and pressure in generator is same as the pressure in
condenser.

It can be seen from Fig.14.2, that as far as the condenser, expansion valve and
evaporators are concerned both compression and absorption systems are identical.
However, the difference lies in the way the refrigerant is compressed to condenser
pressure. In vapour compression refrigeration systems the vapour is compressed
mechanically using the compressor, where as in absorption system the vapour is first

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converted into a liquid and then the liquid is pumped to condenser pressure using the
solution pump. Since for the same pressure difference, work input required to pump a
liquid (solution) is much less than the work required for compressing a vapour due to
Pc
very small specific volume of liquid ( w = − ∫ v.dP ), the mechanical energy required to
Pe
operate vapour absorption refrigeration system is much less than that required to
operate a compression system. However, the absorption system requires a relatively
large amount of low-grade thermal energy at generator temperature to generate
refrigerant vapour from the solution in generator. Thus while the energy input is in the
form of mechanical energy in vapour compression refrigeration systems, it is mainly
in the form of thermal energy in case of absorption systems. The solution pump work
is often negligible compared to the generator heat input. Thus the COPs for
compression and absorption systems are given by:

Qe
COPVCRS = (14.1)
Wc

Qe Q
COPVARS = ≈ e (14.2)
Q g + Wp Q g

Thus absorption systems are advantageous where a large quantity of low-grade

thermal energy is available freely at required temperature. However, it will be seen
that for the refrigeration and heat rejection temperatures, the COP of vapour
compression refrigeration system will be much higher than the COP of an absorption
system as a high grade mechanical energy is used in the former, while a low-grade
thermal energy is used in the latter. However, comparing these systems based on
COPs is not fully justified, as mechanical energy is more expensive than thermal
energy. Hence, sometimes the second law (or exergetic) efficiency is used to compare
different refrigeration systems. It is seen that the second law (or exergetic) efficiency
of absorption system is of the same order as that of a compression system.

14.3. Maximum COP of ideal absorption refrigeration system

In case of a single stage compression refrigeration system operating between
constant evaporator and condenser temperatures, the maximum possible COP is given
by Carnot COP:

Te
COPCarnot = (14.3)
Tc − Te

If we assume that heat rejection at the absorber and condenser takes place at
same external heat sink temperature To, then a vapour absorption refrigeration system
operates between three temperature levels, Tg, To and Te. The maximum possible COP
of a refrigeration system operating between three temperature levels can be obtained
by applying first and second laws of thermodynamics to the system. Figure 14.3
shows the various energy transfers and the corresponding temperatures in an
absorption refrigeration system.

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 Tg
Pump
Wp
Qg

Cycle
System
Qa + Qc

Qe
Te TT
o∞

Fig.14.3: Various energy transfers in a vapour absorption refrigeration system

From first law of thermodynamics,

Q e + Q g − Q c + a + Wp = 0 (14.4)

where Qe is the heat transferred to the absorption system at evaporator temperature Te,
Qg is the heat transferred to the generator of the absorption system at temperature Tg,
Qa+c is the heat transferred from the absorber and condenser of the absorption system
at temperature To and Wp is the work input to the solution pump.

From second law of thermodynamics,

ΔS total = ΔS sys + ΔS surr ≥ 0 (14.5)

where ΔStotal is the total entropy change which is equal to the sum of entropy change
of the system ΔSsys and entropy change of the surroundings ΔSsurr. Since the
refrigeration system operates in a closed cycle, the entropy change of the working
fluid of the system undergoing the cycle is zero, i.e., ΔS sys = 0 . The entropy change
of the surroundings is given by:

Q e Q g Q a +c
ΔS surr = − − + ≥0 (14.6)
Te Tg To
Substituting the expression for first law of thermodynamics in the above equation

⎛ Tg − To ⎞ ⎛ ⎞
Qg ⎜ ⎟ ≥ Q e ⎜ To − Te ⎟⎟ − Wp (14.7)
⎜ Tg ⎟ ⎜ T
⎝ ⎠ ⎝ e ⎠

Neglecting solution pump work, Wp; the COP of VARS is given by:

Qe ⎛ Te ⎞⎛ Tg − To ⎞
COPVARS = ≤ ⎜⎜ ⎟⎟⎜ ⎟ (14.8)
⎜ ⎟
Qg ⎝ To − Te ⎠⎝ Tg ⎠

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An ideal vapour absorption refrigeration system is totally reversible (i.e., both
internally and externally reversible). For a completely reversible system the total
entropy change (system+surroundings) is zero according to second law, hence for an
ideal VARS ΔS total, rev = 0 ⇒ ΔS surr , rev = 0 . Hence:
Q e Q g Q a +c
ΔS surr , rev = − − + =0 (14.9)
Te Tg To
Hence combining first and second laws and neglecting pump work, the maximum
possible COP of an ideal VARS system is given by:
Q ⎛ Te ⎞⎛ Tg − To ⎞
COPideal VARS = e = ⎜⎜ ⎟⎟⎜ ⎟ (14.10)
⎜ ⎟
Qg ⎝ To − Te ⎠⎝ Tg ⎠
Thus the ideal COP is only a function of operating temperatures similar to Carnot
system. It can be seen from the above expression that the ideal COP of VARS system
is equal to the product of efficiency of a Carnot heat engine operating between Tg and
To and COP of a Carnot refrigeration system operating between To and Te, i.e.,

Qe ⎛ Te ⎞⎛ Tg − To ⎞
COPideal VARS = = ⎜⎜ ⎟⎟⎜ ⎟ = COPCarnot .η Carnot (14.11)
⎜ ⎟
Qg ⎝ To − Te ⎠⎝ Tg ⎠

Thus an ideal vapour absorption refrigeration system can be considered to be a

combined system consisting of a Carnot heat engine and a Carnot refrigerator as
shown in Fig.14.4. Thus the COP of an ideal VARS increases as generator
temperature (Tg) and evaporator temperature (Te) increase and heat rejection
temperature (To) decreases. However, the COP of actual VARS will be much less
than that of an ideal VARS due to various internal and external irreversibilities
present in actual systems.

Tg
Qg

E WE

Qa
TT∞o

Qc

WE R
Qe
Te

Fig.14.4: Vapour absorption refrigeration system as a combination of a heat

Vapour absorption system as and
engine a combination of Heat Engine and
a refrigerator

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14.4. Properties of refrigerant-absorbent mixtures
The solution used in absorption refrigeration systems may be considered as a
homogeneous binary mixture of refrigerant and absorbent. Depending upon the
boiling point difference between refrigerant and absorbent and the operating
temperatures, one may encounter a pure refrigerant vapour or a mixture of refrigerant
and absorbent vapour in generator of the absorption system. Unlike pure substances,
the thermodynamic state of a binary mixture (in liquid or vapour phase) cannot be
fixed by pressure and temperature alone. According to Gibbs’ phase rule, one more
parameter in addition to temperature and pressure is required to completely fix the
thermodynamic state. Generally, the composition of the mixture is taken as the third
independent parameter. The composition of a mixture can be expressed either in mass
fraction or in mole fraction. The mass fraction of components 1 and 2 in a binary
mixture are given by:

m1 m2
ξ1 = ; ξ2 = (14.12)
m1 + m 2 m1 + m 2

where m1 and m2 are the mass of components 1 and 2, respectively

The mole fraction of components 1 and 2 in a binary mixture are given by:

n1 n2
x1 = ; x2 = (14.13)
n1 + n 2 n1 + n 2
where n1 and n2 are the number of moles of components 1 and 2, respectively

An important property of a mixture is its miscibility. A mixture is said to be

completely miscible if a homogeneous mixture can be formed through any arbitrary
range of concentration values. Miscibility of mixtures is influenced by the
temperature at which they are mixed. Some mixtures are miscible under certain
conditions and immiscible at other conditions. The refrigerant-absorbent mixtures
used in absorption refrigeration systems must be completely miscible under all
conditions both in liquid and vapour phases.

14.4.1. Ideal, homogeneous binary mixtures

A binary mixture of components 1 and 2 is called as an ideal mixture, when it

satisfies the following conditions.

Condition 1: The volume of the mixture is equal to the sum of the volumes of its
constituents, i.e., upon mixing there is neither contraction nor expansion. Thus the
specific volume of the mixture, v is given by:

v = ξ1 .v1 + ξ 2 .v 2 (14.14)

where ξ1 and ξ2 are the mass fractions of components 1 and 2. For a binary mixture,
ξ1 and ξ2 are related by:
ξ1 + ξ 2 = 1 ⇒ ξ 2 = 1 − ξ1 (14.15)

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Condition 2: Neither heat is generated nor absorbed upon mixing, i.e., the heat of
solution is zero. Then the specific enthalpy of the mixture, h is given by:

h = ξ1 .h 1 + ξ 2 .h 2 = ξ1 .h 1 + (1 − ξ1 )h 2 (14.16)

Condition 3: The mixture obeys Raoult’s law in liquid phase, i.e., the vapour pressure
exerted by components 1 and 2 (Pv,1 and Pv,2) at a temperature T are given by:

Pv ,1 = x 1 .P1,sat (14.17)
Pv , 2 = x 2 .P2,sat (14.18)

where x1 and x2 are the mole fractions of components 1 and 2 in solution, and P1,sat
and P2, sat are the saturation pressures of pure components 1 and 2 at temperature T.
The mole fractions x1 and x2 are related by:

x 1 + x 2 =1⇒ x 2 =1 − x 1 (14.19)

Condition 4: The mixture obeys Dalton’s law in vapour phase; i.e., the vapour
pressure exerted by components 1 and 2 (Pv,1 and Pv,2) in vapour phase at a
temperature T are given by:

Pv ,1 = y 1 .Ptotal (14.20)
Pv , 2 = y 2 .Ptotal (14.21)

where y1 and y2 are the vapour phase mole fractions of components 1 and 2 and Ptotal
is the total pressure exerted at temperature T. The vapour phase mole fractions y1 and
y2 are related by:

y1 + y 2 = 1 ⇒ y 2 = 1 − y1 (14.22)

and the total pressure Ptotal is given by:

Ptotal = Pv ,1 + Pv , 2 (14.23)

If one of the components, say component 2 is non-volatile compared to component

1(e.g. component 1 is water and component 2 is lithium bromide salt), then y1 ≈ 1 and
y2 ≈ 0, Pv,2 ≈ 0, then from Raoult’s and to Dalton’s laws:

Ptotal ≈ Pv,1 = x 1 .P1,sat (14.24)

14.4.2. Real mixtures

Real mixtures deviate from ideal mixtures since:

1. A real solution either contracts or expands upon mixing, i.e.,

v ≠ ξ1 .v1 + ξ 2 .v 2 (14.25)

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2. Either heat is evolved (exothermic) or heat is absorbed upon mixing;

h = ξ1 .h 1 + (1 − ξ1 )h 2 + Δh mix (14.26)

where Δhmix is the heat of mixing, which is taken as negative when heat is evolved
and positive when heat is absorbed.

The above two differences between ideal and real mixtures can be attributed to
the deviation of real mixtures from Raoult’s law. Real mixtures approach ideal
mixtures as the mole fraction of the component contributing to vapour pressure
approaches unity, i.e., for very dilute solutions. Figure 14.5 shows the equilibrium
pressure variation with liquid phase mole fraction (x) of ideal and real binary mixtures
with positive (+ve) and negative deviations (-ve) from Raoult’s law at a constant
temperature. It can be seen that when the deviation from Raoult’s law is positive
(+ve), the equilibrium vapour pressure will be higher than that predicted by Raoult’s
law, consequently at a given pressure and composition, the equilibrium temperature of
solution will be lower than that predicted by Raoult’s law. The converse is true for
solutions with –ve deviation from Raoult’s law, i.e., the equilibrium temperature at a
given pressure and composition will be higher than that predicted by Raoult’s law for
solution with negative deviation. This behaviour can also be shown on specific
enthalpy-composition diagram as shown in Fig. 14.6 for a solution with negative
deviation from Raoult’s law. Refrigerant-absorbent mixtures used in vapour
absorption refrigeration systems exhibit a negative deviation from Raoult’s law, i.e.,
the process of absorption is exothermic with a negative heat of mixing.

T = Constant

P1,sat

+ve

P Ideal

-ve P2,sat

0 1
x2

Fig.14.5: Pressure-concentration behaviour of ideal and real mixtures at a constant

temperature

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 T = Constant

h1
Ideal solution

Δhmix
h2

Real solution

0 1
ξ2

Fig.14.6: Enthalpy-concentration behaviour of an ideal mixture and a real mixture with

negative deviation from Raoult’s law

14.5. Basic Vapour Absorption Refrigeration System

Figure 14.7 shows a basic vapour absorption refrigeration system with a
solution heat exchanger on a pressure vs temperature diagram. As shown in the figure,
low temperature and low pressure refrigerant vapour from evaporator at state 1 enters
the absorber and is absorbed by solution weak in refrigerant (state 8). The heat of
absorption (Qa) is rejected to an external heat sink at T∞. The solution, rich in
refrigerant (state 2) is pumped to the generator pressure (Pg) by the solution pump
(state 3). The pressurized solution gets heated up sensibly as it flows through the
solution heat exchanger by extracting heat from hot solution coming from generator
(state 4). Heat is supplied to this solution from an external heat source in the generator
(Qg at Tg), as a result refrigerant vapour is generated (absorbent may also boil to give
off vapour in case of ammonia-water systems) at state 5. This high-pressure
refrigerant vapour condenses in the condenser by rejecting heat of condensation to the
external heat sink (Qc at T∞) and leaves the condenser as a high pressure liquid (state
9). This high pressure refrigerant liquid is throttled in the expansion device to
evaporator pressure Pe (state 10) from where it enters the evaporator, extracts heat
from low temperature heat source (Qe at Te) and leaves the evaporator as vapour at
state 1, completing a cycle. The hot solution that is weak in refrigerant (state 6) leaves
the generator at high temperature and is cooled sensibly by rejecting heat to the
solution going to the generator in the solution heat exchanger (state 7). Then it is
throttled to the evaporator pressure in the throttle valve (state 8), from where it enters
the absorber to complete the cycle. It can be seen that though not an essential
component, the solution heat exchanger is used in practical systems to improve the
COP by reducing the heat input in the generator. A solution heat exchanger as shown
in Fig.14.7 is a counterflow heat exchanger in which the hot solution coming from the
generator comes in thermal contact with the cold solution going to the generator. As a

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 result of this heat exchange, less heat input is required in the generator and less heat is
rejected in the absorber, thus improving the system performance significantly.

P
Pg 5
Condenser Generator
Qg
6
Qc
9 4
Heat exchanger
7
10 3
8
Pe Evaporator Absorber
1
Qe 2

Qa Solution pump

Te T∞ Tg T
Fig.14.7: Basic
Basic vapour
vapour absorption
absorption refrigeration
refrigeration system
system withwith a solution
solution heat exchanger on a
heat exchanger
pressure vs temperature diagram

The thermodynamic performance of the above system can be evaluated by

applying mass and energy balance to each component assuming a steady flow
process. In simple theoretical analyses, internal irreversibilities such as pressure drops
between the components are generally neglected. To find the performance from the
mass and energy balance equations one needs to know inputs such as the type of
refrigerant-absorbent mixtures used in the system, operating temperatures,
composition of solution at the entry and exit of absorber, effectiveness of solution
heat exchanger etc. A simple steady flow analysis of the system will be presented in
later sections.

14.6. Refrigerant-absorbent combinations for VARS

The desirable properties of refrigerant-absorbent mixtures for VARS are:

i. The refrigerant should exhibit high solubility with solution in the absorber.
This is to say that it should exhibit negative deviation from Raoult’s law at
absorber.
ii. There should be large difference in the boiling points of refrigerant and
absorbent (greater than 200oC), so that only refrigerant is boiled-off in the
generator. This ensures that only pure refrigerant circulates through
refrigerant circuit (condenser-expansion valve-evaporator) leading to
isothermal heat transfer in evaporator and condenser.

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 iii. It should exhibit small heat of mixing so that a high COP can be achieved.
However, this requirement contradicts the first requirement. Hence, in
practice a trade-off is required between solubility and heat of mixing.
iv. The refrigerant-absorbent mixture should have high thermal conductivity
and low viscosity for high performance.
v. It should not undergo crystallization or solidification inside the system.
vi. The mixture should be safe, chemically stable, non-corrosive, inexpensive
and should be available easily.

The most commonly used refrigerant-absorbent pairs in commercial systems are:

1. Water-Lithium Bromide (H2O-LiBr) system for above 0oC applications such

as air conditioning. Here water is the refrigerant and lithium bromide is the
absorbent.
2. Ammonia-Water (NH3-H2O) system for refrigeration applications with
ammonia as refrigerant and water as absorbent.

Of late efforts are being made to develop other refrigerant-absorbent systems

using both natural and synthetic refrigerants to overcome some of the limitations of
(H2O-LiBr) and (NH3-H2O) systems.

Currently, large water-lithium bromide (H2O-LiBr) systems are extensively

used in air conditioning applications, where as large ammonia-water (NH3-H2O)
systems are used in refrigeration applications, while small ammonia-water systems
with a third inert gas are used in a pumpless form in small domestic refrigerators
(triple fluid vapour absorption systems).

Questions:
1. Compared to compression systems, absorption systems offer the benefits of:

a) Higher COPs
b) Lower refrigeration temperatures
c) Possibility of using low-grade energy sources
d) All of the above

Ans.: c)

2. Absorption of the refrigerant by the absorbent in a vapour absorption refrigeration

system is accompanied by:

a) Absorption of heat
b) Release of heat
c) No thermal effects
d) Reduction in volume

Ans. b)

3. An absorption system consisting of only two closed vessels:

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a) Can provide continuous refrigeration
b) Provides refrigeration intermittently
c) Can work on solar energy alone
d) Has no practical application

Ans. b) and c)
4. The conventional, continuously operating single stage vapour absorption
refrigeration system:

a) Requires only thermal energy as input

b) Uses a thermal compressor in place of a mechanical compressor
c) Does not require a condenser
d) Consists of two expansion valves

Ans. b) and d)

5. For an ideal refrigerant-absorbent mixture:

a) There is neither expansion nor contraction upon mixing

b) The mixing process is exothermic
c) The mixing process is endothermic
d) Obeys Raoult’s law in liquid phase and Dalton’s law in vapour phase

Ans. a) and d)

6. For a refrigerant-absorbent mixture with a negative deviation from Raoult’s law:

a) The mixing process is exothermic

b) The mixing process is endothermic
c) The actual equilibrium temperature will be less than that predicted by Raoult’s law
d) The actual equilibrium temperature will be less more that predicted by Raoult’s law

Ans. a) and d)

7. Refrigerant-absorbent pairs used in vapour absorption refrigeration systems should:

a) Exhibit negative deviation from Raoult’s law at absorber

b) Exhibit positive deviation from Raoult’s law at absorber
c) Have large heat of mixing
d) Have large boiling point difference between refrigerant and absorbent

Ans. a) and d)

8. Which of the following statements are true:

a) Water-lithium bromide systems are used for refrigeration applications above 0oC
only
b) Ammonia-water systems can be used for refrigeration applications below 0oC only
c) Small ammonia-water systems are used in domestic refrigerators
d) Small water-lithium bromide systems are used in room air conditioners

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Ans. a) and c)

9. The operating temperatures of a single stage vapour absorption refrigeration system

are: generator: 90oC; condenser and absorber: 40oC; evaporator: 0oC. The system has
a refrigeration capacity of 100 kW and the heat input to the system is 160 kW. The
solution pump work is negligible.

a) Find the COP of the system and the total heat rejection rate from the system.

b) An inventor claims that by improving the design of all the components of the
system he could reduce the heat input to the system to 80 kW while keeping the
refrigeration capacity and operating temperatures same as before. Examine the
validity of the claim.

Ans.:
a) COP = Qe/Qg = 100/160 = 0.625 (Ans.)

Total heat rejection rate = Qa+Qc = Qe+Qg = 100 + 160 = 260 kW (Ans.)

b) According to the inventor’s claim, the COPclaim is given by:

COPclaim = Qe/Qg = 100/80 = 1.25

However, for the given temperatures, the maximum possible COP is given by:

⎛Q ⎞ ⎛ Te ⎞⎛⎜ Tg − To ⎞
COPideal VARS = ⎜ e ⎟ = ⎜⎜ ⎟⎟ ⎟
⎜ Qg ⎟ ⎠⎜⎝ Tg ⎟
⎝ ⎠ max ⎝ To − Te ⎠

Substituting the values of operating temperatures, we find that:

⎛ Te ⎞⎛⎜ Tg − To ⎞ ⎛
⎟=⎜ 273 ⎞⎛ 50 ⎞
COPmax = ⎜⎜ ⎟⎟ ⎟⎜ ⎟ = 0.94
⎝ To − Te ⎠⎜⎝ Tg ⎟ ⎝ 313 − 273 ⎠⎝ 363 ⎠
⎠

Since COPclaim > COPmax ⇒ Inventor’s claim is FALSE (Ans.)

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1. The following figure shows a pair of containers A & B. Container B contains an
aqueous solution of (LiBr+H2O) at a mass fraction (xi) of 0.6. Container A and
connecting pipe are filled with pure water vapor. Initially the system (A+B) is at an
equilibrium temperature of 90oC, at which the pressure is found to be 9.0 kPa. Now
water vapour starts condensing in A as cooling water starts flowing through the coil
kept in A.

A B

a) What is the temperature of the coil at which steam starts condensing in A?

b) Does the System pressure remain constant during condensation? If not, how to
maintain the pressure constant at 9.0 kPa? What happens to the temperature of
solution in B?
c) As water vapour condenses in A there will be transfer of water vapour from B
to A resulting in change of mass fraction of solution (Δx) in B. Find a relation
between Δx and f, where f is the ratio of initial mass of solution in B to the
mass of water vapour transferred from B to A.
d) What is the amount of solution required initially in B so that a mass of 1 kg of
water is transferred from B to A with a corresponding change of mass
fraction(Δx) by 0.05?
e) Neglecting the contribution of temperature changes, what is the amount of
heat transferred at A and B during the transfer of 1 kg of water from B to A? Is
energy balanced?
f) What is required to reverse the process so that initial conditions are restored?
g) Show the forward and reverse process on D ring plot.

Use the following data:

Initial enthalpy of solution = 220 kJ/kg; Final enthalpy of solution = 270 kJ/kg
Assume that the average latent heat of vaporization of water and enthalpy of water
vapour = 2500 kJ/kg
Saturation pressure of water vapour (in kPa) is given by the Antoine’s equation:
c1
ln(p sat ) = c o − ; where T is temperature in K, co=16.54, c1=3985, c2=-39.0
T + c2
Ans.:
a) Steam in vessel A starts condensing when the surface temperature of the coil falls
below the saturation temperature of water at 9.0 kPa. Using Antoine’s equation:

3985
ln(9) = 16.54 − ⇒ T = 316 .84 K = 43.7 o C (Ans.)
T − 39

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b) System pressure falls as condensation of water vapour takes place in A. To keep
the system pressure constant, vapour has to be generated in B by supplying heat to
solution in B. Since the solution in B becomes richer in LiBr (i.e., concentration
increases), at the same pressure of 9.0 kPa, the solution temperature in B increases.
(Ans.)

c) From the definition of concentration for H2O-LiBr solution;

⎛ ML ⎞ ⎛ ML ⎞ ⎡ (
M W ,i − M W , f ) ⎤
Δx = x f − x i = ⎜ ⎟−⎜ ⎟ = ML ⎢ ⎥
⎜ ML + M W , f
⎝
⎟ ⎜ ML + M W , i ⎟
⎠ ⎝ ⎠ ( )(
⎣⎢ ML + M W ,i . ML + M W ,i ⎦⎥ )
Amount of water transferred from B to A = (MW,i - MW,f)

The factor f is defined as:

⎛ ML + M W , i ⎞
f =⎜ ⎟
⎜ M W ,i − M W , f ⎟
⎝ ⎠

Substituting the above in the expression for Δx and using the definition of
concentration, we find that:

⎛x ⎞
Δx = x f − x i = ⎜ f ⎟ (Ans.)
⎝ f ⎠

d) Mass of water transferred is 1.0 kg and change in concentration is 0.05. Hence the
final concentration is:

xf = xi + 0.05 = 0.60 + 0.05 = 0.65

Substituting this value in the expression for Δx, we find that

⎛ x ⎞ ⎛ 0.65 ⎞
f =⎜ f ⎟=⎜ ⎟ = 13
⎝ Δx ⎠ ⎝ 0.05 ⎠

Hence the initial mass of solution is given by:

(ML + M W ,i ) = f.(mass of water transferre d) = 13 X 1.0 = 13 kgs (Ans.)

e) From energy balance of vessel B, the amount of energy transferred to B is given

by:

Q B,in = (MB, f .h f − MB,i .hi ) + (M W ,i − M W , f )h W

Substituting the values of enthalpies and initial and final mass of solution (13 kg and
12 kg, respectively), we find that the heat transferred to B is:

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 QB,in = 2880 kJ (Ans.)
Neglecting the heat transferred during initial sensible cooling of vapour, the total heat
transferred at Vessel A is:

QA,out = Amount of water vapour condensed X latent heat of vapourization = 2500 kJ

(Ans.)

The difference in energy transferred at A and B is stored in the form of heat of

solution. (Ans.)

f) To reverse the process and arrive at initial condition, the condensed water in vessel
A has to be vapourized by supplying heat to vessel A. The vapour generated is
absorbed by strong solution in B. Since this is an exothermic process, heat has to be
rejected from B. (Ans.)

g) D˘hring plot of forward and reverse processese is shown below:

P x=0 xi = 0.60 xf = 0.65

i f

T
Forward process

Reverse process

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